Dressing fibrous and textile materials



Patented June 17, 1947 DRESSING FIBROUS AND TEXTILE MATERIALS LeonLllienfeld, deceased, late of Vienna, Germany, by Antonie Lilienfeld,administratrix, Winchester, Mass, assignor to Lilienfeld Patents, Inc.,Boston, Mass., a corporation of Massachusetts No Drawing. ApplicationDecember 22, 1942, Se-

rial No. 469,839. Britain September 7,

39 Claims. 1

This invention relates in general to a process of treating textiles andin particular to a process for coating, pad-dyeing and printing textilefabrics. The invention also includes the production of degradedcellulose derivatives (e. g. ethers) for use in treating textiles, and asolution or dispersion of such degraded cellulose derivatives, fordressing textiles.

In his U. S. Patents Nos. 1,589,606, 1,682,292, 1,682,293, 1,682,294,1,683,831, 1,722,927, 1,722,928, 2,095,524, 2,165,392, 2,231,927,2,265,914 to 2,285,919 and in British Patent 374,964 (corresponding toFrench Patent 715,551, delivered September 29, 1931),the presentinventor has described many types of cellulose ethers which are solublein alkali solution, but insoluble in water.

In these patents he further showed that these alkali soluble,water-insoluble" cellulose ethers can be successfully used for treatingfibrous materials, including textile materials and paper, for coating,impregnating, filling, dressing, weighting, printing, sizing fabrics,yarns, threads, loose fibres or yarn. In the appended claims the termtextile material is intended to embrace yarns, threads, fabrics andpaper.

Furthermore, in his U. S. Patents 1,858,097, 1,910,440,2,021,861,.2,163,607, 2,165,393, 2,265,914, 2,265,915, 2,265,917,2,265,918, 2,296,856 and in British Patents 367,920, 459,122, 462,283,462,456 (and cognate specifications), 462,712, 474,223 and 503,830, hedescribed xanthates of suitable cellulose ethers, including xanthates ofalkali-soluble cellulose ethers, and processes for making such xanthatedethers and methods for treating fibrous material therewith. Thesexanthated ethers are included in the expression xanthates of thoseethers of cellulose in which the content of hy-.

droxyl hydrogen substituted organic radicals is much below one hydroxylhydrogen per one ceHioos-molecular unit of cellulose."

The experience gathered hitherto with regard A to the application ofalkali-soluble cellulose ethers to the treatment of fibrous materialsincluding textile materials has taught that they are very valuable basicmaterials for the production of all finishes in which stifiness or atleast a certain degree of stiffness is required,

On the other hand, the alkali-soluble cellulose ethers share with allother cellulose derivatives 2 soluble in aqueous media, the incapabiityof yielding impregnations, coatings, fillings, dressings, weightings,printings, sizings or any other finishes on fibrous materials, forexample fabrics or yarn which excel by a high degree of softness andtextile appearance. This is due in part to th fact that all the ethersmade heretofore are film-forming and have high viscosities, so that theyinvariably impart a, stiffness to the treated material which isundesirable for some purposes. The term finishing will hereinafter beused to cover this entire group of treatments.

All arduous efforts which have been made with the object of providing ontextiles and other fibrous materials, a permanent and neverthelessperfectly soft finish and which exhibits a soft feel having failed, thelack of a cellulosic material capable of giving a finish which ispermanent, i. e. perfectly (or at least in an appreciable degree) fastto laundering and sufllciently resistant to wear, and which neverthelesshas a feel to the touch that is not inferior or not substantiallyinferior to the feel of the fibrous materials, such as fabrics or yarn,to which it has been applied, is a long felt want in the finishing oftextiles. v

The present invention supplies this desideratum by means ofalkali-soluble, water-insoluble cellulose ethers and, thus, in thetechnology of treating fibrous materials, particularly in the finishingart of textile materials, for example in the art of finishing vegetabletextile materials of natural or artificial origin. For, thepresentinvention produces cellulose ethers which are soluble in aqueous causticalkali solution and insoluble in water and which, when used forfinishing fibrous materials of any kind (especially, however, animal orvegetable or mixed textile materials), yield finishes of any kind thatare sufiiciently permanent and have the desired hand, and this withoutsubstantially altering the textile appearance or their natural softfeel.

The reference in the previous paragraph, to textile materials ofartificial origin is intended to embrace not only natural fibres butalso viscose rayon, cellulose acetate or other cellulose ester threadsand fabrics, nitro-silk (or threads of reduced nitrocellulose),cellulose ether textiles, including the organic solvent soluble andalkali soluble varieties, including those made from xanthates of alkalisolubleethers, cuprammonium threads, and textiles,

made from long chain amines, e. g. nylon. Here the soft feel" of theproduct is also of particular interest.

This novel effect of the present invention i the more surprising andimportant,

(1) since the alkali-soluble cellulose ethers prepared according to thepresent process give this effect even in theabsence of softening agentsor plasticizers, and

(2) since the alkali-soluble cellulose ethers prepared according to thepresent process produce this eifect even when they are introduced intothe fibrous materials in extraordinarily large amounts, for example in aproportion of up to or even up to or 50 percent, or even more,calculated on the weightof the fibrous material.

The present invention resides in the discovery and. recognitionthat,when the degradation of alkali-soluble, water-insoluble cellulose ethersis carried so far that they are deprived of their capacity to formcoherent films or films which do not disintegrate in the coagulatingbath or in the washing water into which they are introduced therefrom,or on being dried or when they are at least made incapable of givingfilms suitable for practical use, but short of becoming soluble i water,there are obtained alkali-sole uble cellulose'ethers which are unusuallyvaluable materials for finishing fibrous materials as herein defined.When such degraded cellulose ethers are applied in the form of theirsolutions or pastes in dilute caustic alkali solution to fibrousmaterials, the ethers do not substantially impair the soft feel of thefibrous materials to which they are applied, and the finishes thusobtained are in most cases relatively fast to commercial laun-.

dering. In addition they do not substantially change the textileappearance of the fibrous materials to which they are applied. Suchtreatment also does not substantially stifien the fibrous materials sotreated. While the invention herein will be described in connection withthe treatment of water insoluble alkali soluble cellulose ethers, theinvention is also applicable to the treatment of other oxy-organocompoimds of cellulose, including in particular, cellulose ether-esters,cellulose esters and cellulose thiourethaneshaving the stated solubilityin caustic alkali solution, and which are insoluble in water.

In all the known processes 'of making cellulose ethers, and in purifyingor isolating same, and in some of the processes of making products(artificial regenerated structures) therefrom, it has long beenrecognized that there was a small amount of degradation of the cellulosemolecule produced, but heretofore the factors in such prior processeshave been such as to prevent any large amount of degradation, because itwas recognized that degrading of the cellulose molecule produced alowering of the quality (wet and dry strength, elasticity, flexibility)of the said structures (films, threads etcI). prime factor in theproduction of soft finishes on textiles resides in the carrying of thedegradation to a controlled and definite extent (short of producingwater solubility), so that the ethers are no longer capable of producingcoherent usable films. Moreover, in order to produce finished textilesthat are laundry-fast, it will be readily understood that the finish onthe textiles must be composed of material which is insoluble in water.

From the foregoing it can be gathered that Now in the present process,the- {organic solvents (alcohol,

one object .of the invention is to prepare and utilize cellulose etherswhich are soluble in dilute caustic alkali solutionbut not in water,andwhich have no capacity to form coherent films or films which do notdisintegrate in the coagulating bath or in the washing water into whichthey are introduced therefrom or on being dried, or alkalisolublecellulose ethers which formfilms that with regard to their properties,are unsuitable for practical use (as films),

that another object of the present invention is to prepare and utilizefinishes as herein defined which do not impair or do not substantiallyimpair, the feel of the fibrous materials as herein defined to whichthey are applied and which are fast (or to an appreciable degree fast)to commercial laundering and sufilciently resistant to wear and tear,and

that the third object of the invention is to supply the art of finishingfibrous materials as herein defined with a cellulosic fibller or loadingmaterial which does not stiffen or does not substantially stifientextile products, and which does not impair or otherwise unfavorablyinfluence the appearance and handle of fibrous materials as hereindefined.

Other objects of the invention will become apparent from the followingdescription.

As far as it, is concerned with the preparation of degradedalkali-soluble, water-insoluble cellulose ethers as herein defined, thepresent invention comprises treating a film-forming alkalisolublewater-insoluble cellulose ether with one or more degrading agents whichare capable of depriving the cellulose ether of its capacity to formcoherent films which do not disintegrate in the coagulating bath or inthe washing water into which they are introduced therefrom or on beingdried, or at least making the cellulose ethers incapableof givingcoherent films suitable for practical use.

A great variety of substances exist, which are well known in the art tobe capable of degrading cellulose ethers, either during or after theforma-- tion and/or isolation of such ethers.

As initial materials in the present invention there may be used anyfilm-forming cellulose ethers which contain not more than one alcoholradical, for example one alkyl group or hydroxyalkyl group, or onehydroxy-acid residue, introduced ether-fashion into the cellulosemolecule per 2 or 3 or 4 or 5 or 15 or 30 or even 50 or moreCaH1oO5-molecular units of cellulose. In the prior literature, thoseethers containing from 2 to about 14 CsHmOs-molecular units of celluloseto one substituent alcohol radical were known as ethers of low degree of,etherification, such ethers being described for example in BritishPatent No. 374,964 and also in the prior literature, those etherscontaining over about 14 (e. g. 15 to 50) CaH1oO5-molecular units ofcellulose per one' substituent alcohol radical linked ether fashion tothe cellulose molecule, have been referredto as ethers of extremely lowdegree of etherification. The latter kind of ethers are shown forexample in British Patent No. 462,- 283. The former class of ethers canusually be dissolved in dilute caustic alkali solution by refrigerationor freezing, and the latter class cannot be so dissolved. Both theseclasses of ethers are insoluble in water and in the usual V benzene,acetone, chloroform, carbon tetrachloride, ethylene chloride, etc.) aswell as in mixtures of such organic solvents with each other, and inmixtures of esters,

-insoluble alkali-soluble non-coherent-film-forming oxy-organoderivatives of cellulose (cellulose ethers) There may also be used asthe initial cellulose ether (for degrading), any of the film-formingalkali-soluble, water-insoluble cellulose ethers described in U. S.Patents 2,265,919, 2,231,927, 2,265,916, 1,858,097, 1,910,440,2,100,010, 2,265,914, 2,265,915, 2,163,607 or 2,296,856, or in BritishPatents 367,920, 462,283 or 503,830, or 374,964.

In other words, not only such film-forming cellulose ethers of theaforementioned types as can be prepared by the processes and methodsdescribed in the patents given above, but also filmforming celluloseethers of the aforementioned types can be used herein, however prepared,can be modified (degraded) and be used in the present invention.

It is further to be understood that, in the present invention, eithersimple or mixed cellulose ethers of the aforementioned types can be usedas initial materials. Asmixed ethers the following may be named .by wayof example. Cellulose ethers containing in their molecule two differentalkyl or hydroxy-alkyl group's, hydroxy-acid residues, or celluloseethers containing in their molecule a plurality of said kinds ofradicals.

The most eiiective' means of converting the film-forming celluloseethers into non-film forming ethers is the treatment of the film-formingcellulose ethers with such agents or mixtures of agents as exert ahydrolyzing and/or degrading and/or oxidizing action on the film-formingcellulose ethers, the conditions, particularly the temperature and/orduration of the treatment being such as to deprive the cellulose ethersof the aforementioned types of their capacity to form coherent films.Such result will be hereinafter referred to, for brevity, as beingsufliciently degraded.

The cellulose ethers degraded to the extent indicated in the precedingparagraph, will hereinafter be termed ,water-insoluble alkali-soluble,non-film-forming cellulose ethers.

Among the hydrolyzing and/or degrading agents which may or may not havean oxidizing efiect on the cellulose ethers of the aforementioned types,substances having an acid reaction, such as acids or acid salts and alsosubstances, for instance salt capable of generating acid, have provedvery suitable for the treatment according to the present invention. Theacids (inorganic and organic) or mixturesof acids may be used in theconcentrated state or in moderately concentrated or preferably dilutestate (i. e. as solutions, e. g. aqueous solutions).

When, instead of acids, one or more acid salts by themselves ortogetherwith one or more acids are used as means of carrying the presentinvention into effect, they may be applied to the cellulose ethers ofthe aforementioned types in concentrated solutions or preferably inmoderately concentrated solutions or in dilute solutions.

As is well known, strong acids or strong solutions of acid salts are farmore powerful as 'degrading agents, applied to cellulosic substances,but dilute solutions of acids or acid salts are more easily controlledin their actions.

Treating the film-forming cellulose ethers with dilute acids is simplerand easier to control than 6 by treating such ethers with concentratedacids. The conversion of the film-forming cellulose ethers into theaforementioned non-fllm-forming types (1. e. the degrading treatment)may be carried out in various ways. Some of these methods are describedin the following lines by way of examples to which, however, the presentinvention is not limited.

First method.--This method consists in treating a film-forming celluloseether with an excess of a dilute mineral acid in the cold, 1. e. at roomtemperature or at a temperature not substantially exceeding roomtemperature or at a temperature below room temperature.

Second method.-Th.is method consists in treating a film-formingcellulose ether with an excess of a dilute mineral acid as in the firstmethod, but at a raised temperature, with or without pressure.

Third method-This method consists in impregnating or otherwise mixing afilm-forming cellulose ether with an excess of a dilute mineral acid ofthe types described in the first method at room temperature, removingthe excess of the acid by pressing, centrifuging or the like (butwithout washing), dryin the pressed and prefably comminuted material andthen leaving it in the air (e. g. at room temperature), until theconversion is sufficiently eii'ected, or the material after being.pressed may be heated until the cellulose ether becomes sufiicientlyconverted.

In the foregoing methods, instead of the acids, also aqueous solutionsof acid salts, for example of bisulphates or bisulphites can be used,and also such salts of inorganic acids as exert acid action by way ofhydrolysis in their aqueous solutions, for example aluminum sulphate ormagnesium chloride or zinc chloride or alkali chlorides or the, like;

Particularly, when they are conducted at a raised temperature, in theforegoing three methods, instead of the mineral acids, organic acids,

for example formic acid, acetic acid, oxalic acid or an hydroxy-acid,for example glycollic acid, lactic acid, tartaric acid, citric acid orthe like, by themselves or in mixture with mineral acids may'be used.When the organic acids are used by themselves, the concentrations mustbe higher than the concentrations of the mineral acids. In some cases itis possible to attain the desired result according to the presentinvention by treating the cellulose ether with a concentrated organicacid, for example with glacial acetic acid, optionally in the heat.

Fourth method.'I'his method consists in treating the film-formingcellulose ether preferably with stirring or otherwise agitating, withstrong sulphuric acid of a concentration which is incapable ofdissolving the cellulose ether or a substantial part thereof. Fifthmeth0l.-This method consists in treating, preferably with stirring orotherwise agitatin a film-forming cellulose ether, at room temperatureor at a temperature not substantially exceeding room temperature withstrong hydrochloric acid'e. g. of 33 to 34 per cent strength until thecellulose ether becomes sufliciently converted. In general, the desiredresult according to the present invention is attained after acomparatively long treatment, for example after 12 to 24 hours orlonger.

Sixth meth0d.This method consists in treating a film-forming celluloseether, at a temperature not substantially exceeding room temperature orat a temperature below room temperature with gaseous hydrochloric acidin presence The water may be introduced either by using the gaseoushydrochloric acid in the moist state (which is the case when the gaseoushydrochloric acid is not dried before coming in contact with thecellulose ether), or by usin a parent cellulose ether containingmoisture or by moistening the parent cellulose ether.

This method can also be carried out at a raised temperature, for exampleat 40 to 100 0., for example in such a manner that the cellulose isfirst saturated with the gaseous hydrochloric acid and then transferredto a closed vessel. for example a pressure vessel and heated to 40 to100 C., until the cellulose ether becomes sufiiciently converted.

Seventh methd.-This method consists in treating a film-forming celluloseether, in the presence of alkali, for example in the presence of acaustic soda solution of 18 to 20 per cent strength with a smallproportion (for example 0.2 to 2 per cent) of chlorine or bromine untilthe cellulose ether becomes sufficiently converted.

Eighth method.This method consists in treating a film-forming celluloseether with chlorine or bromine in the presence of water, which may beintroduced as described in the sixth method, until the cellulose etherbecomes sufficiently converted. (In presence of. water the chlorineexerts a 'hydrolyzing or degrading and oxidizing action on the celluloseethen).

Ninth method.This method consists in treating a film-forming celluloseether with a strong organic acid, for example glacial acetic acid,containing chlorine or bromine, at a raised temperature preferably at atemperature of 30 to 80 0., until the cellulose ether becomessufficiently converted.

In all the nine methods described above, after the treatment iscompleted, the product must be washed with water or alcohol or the likeuntil free from acid, and free from the other reagents used.

Regardless of whether the hydrolyzing or degrading or hydrolyzing andoxidizing or degrading and oxidizing agents, particularly acids, are

used in the concentrated or more or less diluted state, care must betaken that the treatment is carried out under such conditions as toensure the production of a cellulose ether which is substantially whollysoluble in refrigerated aqueous 'caustic alkali solution or at leastsubstantially dispersible therein, which is insoluble or only soluble ina minor proportion in water and which is incapable of forming coherentfilms" as above described, (1. e. until the ether becomes-sunlcientlyconverted").

The degrading should be stopped before too much (say 30-50%) of theweight of the initial cellulose ether of the degraded product becomeswater-soluble.

Since the paramount factors giving the desired result (sufiicientconversion), are either the time of the treatment or the temperature ofthe treatmen or both, to obtain the desired result, it is necessary toadapt the time of the treatment to the temperature and vice versa. Andthese factors are both influenced by the concentration and degree ofactivity of the acid or other reagent or reagents used for theconversion.

To find out the exact or approximate time for the endpoint of thetreatment, a sample of the cellulose ether under treatment is withdrawn,washed with water and then contacted with a solvent or dispersion mediumfor the alkali-soluble cellulose ether, particularly with a caustic sodasolution of '1 to 10 per cent at room temperature or at a lowertemperature, for example at 0 C., or below 0 C., for-example at minus 5to minus 10 C. The thus obtained complete or incomplete or partialsolution or dispersion or paste or swollen mass or magma is then testedfor film-forming properties, e. g., by being spread on a glass plate andimmersed in a coagulatin bath, for example in dilute acid, for examplein sulphuric acid of 10% strength that may or may not contain sodiumsulphate or magnesium sulphate or in a solution of a salt, for examplein a strong solution of ammonium sulphate or ammonium chloride. If it isdesired to obtain a cellulose ether which is incapable of forming acoherent film, then the endpoint is reached as soon as the cellulosether under treatment gives a solution or dispersion or paste or magma ormass, which spread on the glass plate and coagulated, does not form afilm, for instance when it disintegrates in the coagulating bath, orforms therein only crumblesor a pasty or sticky mass, or isdisintegrated during washing or during drying. I

In some cases, particularly when a, far-going degradation is aimed at,the physical condition of the washed and preferably dried product mayserve as a guiding line with regard to the question whether or not thedesired endpoint is reached. For example, if after a certain time oftreatment the cellulose ether has become more or less friable, forinstance if it can be easily pulverized or easily crushed or ground, thetreatment can be regarded as completed.

When the endpoint or endpoints of the treatment of a certain type ofcellulose ether with a certain degrading or hydrolyzing agent, forexample acid, of a certain concentration and at a certain temperatureare determined by-one or more preliminary experiments as describedabove, no further preliminary experiments are necessary if it is desiredto produce a degradation product of a cellulose ether of theaforementioned types having the desired properties by means of the verysame treatment with the very same materials and-at the same temperature,

Since also other substances or mixtures of substances or other materialsand also some physical means (for example, heating with or withoutpressure in absence or presence of organic or inorganic substances, suchas water or glycerine or oils or liquid or solid hydrocarbons, salts,etc., until the cellulose ether becomes incapable -.of forming coherentfilms or films which do not disintegrate in the coagulating bath or inthe washing water into which they are introduced therefrom or on beingdried or until the cellulose ether becomes incapable of giving filmssuitable for practical use) substances can be used as degrading agents,which in chemistry are known as hydrolyzing or as degrading or ashydrolyzing and degrading agents, can also be used in the presentinvention for the treatment of the cellulose ethers of theaforementioned types, it must be expressly stated that it is notintended to limit that modification of the carrying out of the presentinvention in practice in which the cellulose ethers of theaforementioned types are treated with hydrolyzing or degrading orhydrolyzing and degrading media to the treatment of the said celluloseethers with a hydrolyzing or degrading or hydrolyzin'g and'degradingagent way of examples to which the present invention containing one ormore acid substances such as V I degraded cellulose derivative is onethat will disent invention, a few oxidizing agents being, by

is not limited, set forth in the following lines.

(1) Chloride of lime (bleaching powder), preferably in a solution of 2to Be. at room temperature or at a raised temperature, for-example of 30to. 100 0., with or without subse quent treatment with carbonic acid forwhich treatment air or carbonic acid produced chemically or chimneygases or lime-kiln gases, may be used.

(2) Hypochlorous acid or a hypochlorite of an 'alkali metal, such assodium hypochlorite, preferably in solution, at room temperature or at araised temperature or at a temperature below room temperature. Ifhypochlorous acid is used,

it may be caused to act on the cellulose ether in the direct or in theindirect manner, for example by conducting an electric current through asuspension of the cellulose ether in an aqueous solution of potassiumchloride, which is neutral at the beginnin of. the treatment.

(3) A solution of chlorine or bromine in water at room temperature orata raised temperature or at a temperature below room temperature.

' (4) Chlorine in presence of sunlight and water at room temperature orat-a raised temperature or at a temperature below room temperature.

(5) Potassium permanganate at room tem- I perature or at a raisedtemperature or at a temperature below room temperature, preferably insolution, for example of 1.5 to 4 per cent strength in the absence orpresence of an alkali, such as caustic soda.

(6) Nitric acid at room temperature or at a raised temperatureor at atemperature below room temperature.

(7) Chromic acid, for example in the form of potassium bichromate andsulphuric acid. I

'(8) Strong caustic soda solution (for example of to 50 per cent) hotand in presence of oxygen. For this purpose the oxygen of the air orchemically produced oxygen can be used.

(9) Hydrogen peroxide or an alkali peroxide in a concentrated or dilutesolution at room temperature or at a raised temperature or at atemperature below room temperature. In some cases, also ozone can beused in the present invention.

For the production of finishes as herein defined. the process comprisesapplying to a fibrous material a solution of a degraded cellulose etherin an aqueous caustic alkali solution, then squeezing out excess of saidsolution, then treating the sotreated textile with a setting orcoagulating bath, then washing and drying. Instead of a solution, amagma, suspension, dispersion or paste can be used. Instead of adegraded cellulose ether, other degraded cellulose derivatives, such asesters, thiouretanes, etc., can be used. The term oxyorgano derivativeof cellulose being hereinafter used to cover such group of substances.The caustic alkali solution can conveniently be a 6-10% NaOH solution inwater. One or several of the degraded cellulose oxy-organo bodies may beused. The solution may be made at room temperature, if the cellulosederivative used will dissolve at such temperature, but preferably thesolve only; at a much lower temperature, e. g.,. 4

-15 to +5 O. Inplace of some or all of the caustic alkali, a. solutionof a strong organic base,

' e. g., guanadine, or a quaternary base or a derivative thereof, or anammonia derivative of carbon dioxide .(e. g. urea, cyanamid,- thiourea,dicyanamid) or a solution of a thiocyanate, can be used as the solventor dispersion medium. With the solution etc., of the degraded celluloseether, other colloids such as alkali soluble cellulose derivatives, e.g., ethers, or viscose or starch or dextrine or any compatible sizing,fordressing textiles, canbe used. The fibrous material to be finishedmay be loose fibres, yarns, threads,

fleeces, fabrics, paper or the like, of natural (Vegetable'or-animal) orartificial or synthetic origin, (e. cotton, wool, linen, flax, hemp,ramie, Jute, rayon, etc).

The setting or coagulating bath may be any of those commonly used in theproduction of regenerated articles from viscose.

' Thus, for instance, coagulating or precipitat ing baths containing anacid or'an acid salt or one of these with a neutral salt of a monovalentor divalent or trivalent metal or a solution of one or more neutralsalts, for example a solution of ammonium chloride or of ammoniumsulphate,

or of an alkali metal chloride or the like, which baths may or may notcontain an organic substance, for instance glucose or glycerine, may besuccessfully used in the present invention as coagulating orprecipitating baths.

Also water or solutions of normal alkali carbonates or alkalibicarbonates or carbonated water can be used in the present invention ascoagulating or precipitating baths. These baths offer the possibility ofrecovering at least part of the caustic alkali contained in the solutionof the cellulose ether prepared according to the present invention andin the case of the alkali carbonates also at least part,of thecoagulating agent.

The inventor has further found that, when cellulose ethers of the verylowest degree of etherification. i. e. cellulose ethers which cannot bedissolved in caustic alkali solution (even by freezing) and areinsoluble both in water and in organic solvents, are treated accordingto the present process, they can be also successfully used for treatingtextile materials, for example for the production of finishes as hereindefined. The ethers considered in this paragraph are characterized ashaving a great number of Col-[1005- molecular units of cellulose to onesubstituted alcohol group, e. g., such low-alkyl ethers of cellulose ascontain not substantially below 15 (and often 20 to 50 or more)CsH1oO5-molecular units of cellulose, (to 1 methyl or ethyl group) asdescribed in British Patent N 0. 462,283. Such ethers are of asubstantially lower degree of substitution than those described inBritish Patent 374,964.

The'present invention further embraces the discovery that, on beingxanthated, e. g.treated with carbon bisulphide in presence of causticalkali, the cellulose ethers degraded according to the present inventionyield xanthates which, when applied to fibrous materials of any kindyield finishes that in many cases are far softer than the finishes,obtained with the cellulose ether xanthates known hitherto.

The present invention is important because it makes it possible for thefirst time to convert yarn or fabric which has a certain fullness,density, thickness and weight into a yarn or 11 fabric which has agreater and even far eater. fullness, density, thickness and weight, andwhich yarn and fabric in regard to the softness of their feel, theirlack of stiffness, their appearance and their dyeing properties are notsubstantially different from the yarn or fabric before treatmentaccording to the present invention and which yarn and fabricatesubstantially fast to commercial laundering and sufllciently resistantto wear.

The present invention further enables one to impregnateor fill loosefibres (for example in the form of a fleece) with a cellulosic material,thus, giving fibres which, according to the nature and properties of thecellulose ether used for the impregnation or filling may be in aconglutinated or non-conglutinated condition, and which also are soft tothe touch, suffilciently fast to laundering and which, if in aconglutinated condition, can be worked up into useful articles and, ifin the non-conglutinated state, can be even spun and, if desired,thereafter woven into fabrics or knitted into knitted goods.

It is possible, according to the present invention, to produce noveltextile materials, cheaper than textile materials which, owing to alarger amount of textile fibres contained therein, have the samefullness, density, weight and thickness and which, with regard toappearance, feel and fastness are not substantially superior to thetextile material-s treated according to the present invention.

The degraded cellulose derivatives of the present invention may be alsoused in conjunction with other dressings applied to textile material, e.g. colloidal or binding substances of cellulose or non-cellulosicnature, for instance, cellulose precipitated from cellulose solutions(including viscose, and solutions of cellulose in cuprammonia, urea,thiourea, cyanates or others), starch, dextrine, tragasol, etc.

In this modification of the present process the cellulose ethersproduced according to the present invention are capable of accomplishingthe following two tasks' different from each other:

1) Insofar as they are added to a solution of a colloidal substance ofcellulosic or non-cellulosic nature, in which solution they areinsoluble or only scarcely soluble, they act as pigment or filler or asa loading material.

(2) Insofar as they are added to a solution of a colloid or of acolloidal substance of cellulosic or non-cellulosic nature in which theyare soluble or partially soluble or in which they can be made soluble orpartially soluble by an. appropriate method or process, (e. g. withviscose) they act as a dissolved or partially dissolved admixture to thesolution of the colloidal substance. When used as fillers, the celluloseethers prepared according to the present process are superior to themineral fillers (such as china clay, zinc white. talc (French chalk),lithopone, etc.) and the organic fillers (such as powdered cellulose orthe like) used heretofore in the finishing art. For, owing to theirsoftness and flexibility, they do not substantially stiffen the textilefinishes compared with inorganic ,or organic fillers known hitherto and,owing to their physical character, they do not occupy the surface of,and, thus, do not overlie the fibres of the treated material.Consequently, contrary to all fillers known hitherto, they do notdisguise the true nature and appearance of the fibrous materials, suchas fab rics, knitted goods, yarn. paper, loose fibres, etc., but in mostcases improve their appearance and their density.

Owing to their physical nature, particularly their softness andflexibility, the degraded cellulose ethers are easier fixable on and inthe textile material, than the hard and rigid mineral or organic fillersused hitherto. The resistance to mechanical rubbing, bending, etc. ofthe finishes produced thereby is in some cases greater than theresistance of the finishes of equal covering power produced by means ofthe mineral and. organic fillers used hitherto. And, last but not least,the voluminosity of the cellulose ethers produced according to thepresent invention in their solid state is so much greater than thevoluminosity of the mineral or organic fillers used hitherto, that it ispossible to produce finishes with far smaller proportions (by weight) ofthe present degraded cellulose ethers used as fillers, than theproportions of the hitherto used mineral or organic fillers necessaryfor the preparation of finishes exhibiting the same covering power.

Since the lack of fillers capable of giving the qualities specifiedabove is a long-felt want in the finishing art, besides the desideratumwhich they supply to the art of finishing fibrous materials as hereindefined when used in their dissolved or semi-dissolved state for theproduction of finishes as herein defined, the cellulose ethers degradedas herein described, supply another desideratum in the art of finishingfibrous materials, when used in their solid state as fillers forfinishing materials.

When the present alkali-soluble water-insoluble degraded celluloseethers are not used as fillers but are used in compatible admixture withanother finishing material as herein defined, they contribute towardsits binding effect, to its fastness towards laundering and resistance towear.

When a mineral filler is added to the solution comprising the compatibleadmixture of the degraded cellulose ether and the known finishingmaterial present, the degraded cellulose ether cooperates with the othercolloidal finishing agent in binding or fixing the mineral filler inquestion.

From this it can be seen that, if desired, modification (1) may becombined with modification (2). that is to say, a cellulose etherprepared according to the present invention may be dissolved or at leastpartially dissolved in a solution of another colloidal substancesuitable for finishing fibrous materials as herein defined and to thissolution there may be added a smaller or larger proportion of the samecellulose ether in a finely divided but solid state under suchconditions that no dissolution of the cellulose ether thus added takesplace or dissolution of only part thereof takes place, and that it orthe undissolved part can act as a soft filler.

The application of the solutions or dispersions of the cellulose ethersprepared as above, to the fibrous materials may be accomplished bywholly or partially coating, impregnating, padding or printing orotherwise covering or imbuing a fibrous material as herein defined withthe solution or dispersion, with or without intermediate drying,treating the material with a coagulating bath, either by introducing thematerial into the coagulating bath or by spraying the coagulating liquidon the material, or by conducting the material through a mist of thecoagulating liquid or by any other method of applying a liquid to afibrous material as herein defined, particularly to a textile materialas herein defined.

In U. S. Patents Nos. 1,722,928, 1,682,293, 2,265,917, 2,265,918,2,231,927, 2,265,916, and 2,224,874 andin British Patents 374,964,459,122,

462,712, 462,456 (including cognate specifications) and 474,223,processesof. applying solutions of alkali-soluble cellulose ethers(which are not considerably degraded) to fibrous materials, aredescribed and illustrated by many examples. The degraded celluloseethers prepared according to the present invention may be applied (e. g.in solution) to fibrous materials by any of the methods shown in saidprior patents.

Any suitable softening agent, such as glycerine or a glycol or a sugar,such as glucose or a soap or Turkey red oil, or a drying or non-dryingoil, or a halogen derivative of a dior polyvalent alcohol,' particularlya halohydrln, such as a dichlorohydrin or a monochlorohydrin or ethylenechloroh'ydrin, (in short, in so far as it is compatible with thecellulose ethers prepared according to the present invention, anysubstance knownin the art of alkali-soluble cellulose ethers or in theviscose art as additions to viscose or to solutions of alkali-solublecellulose ethers),-

may be added to the solutions or dispersions of the degraded celluloseethers, prior to or during their application thereof to the fibrous ortextil materials.

As stated above, valuable products which i. e. are also suitable forfinishing as herein defined, can be obtained when the. cellulose ethersdegraded according to the present invention are xanthated, for exampleaccording to the processes described in U. S. Patents Nos. 2,021,861,1,858,097,

1,910,440,'2,265,914, 2,265,915, 2,163,607, 2,265,917, 2,296,856,2,265,918, and 2,296,857 and British Pat ents 367,920, 459,122, 462,283,462,456 (and cogs nated cases), 462,712, 472,888 and 472,933.

The carrying out of the modification of. the

present invention in which the degraded cellulose ethers are usedasfillers is very simple. It consists in adding the degraded celluloseether in the solid moist or dry state, and preferably finely divided toa solution or dispersion of a colloidal or binding substance, which maybe of cellulosic or non-cellulosic nature, and which is suitable for theproduction of finishes as herein defined. Be-

, sides the cellulose ether in the solid state, also other fillers, suchas china clay, talc, zinc white, lithopone, barium sulphate, etc., maybe used.

In order to more completely explain the present invention, the followingspecific examples are given. It is to be understood that the inventionis not limited to these examples, to the precise proportions ofingredients, the times and temperatures and sequences of steps setforth. Parts are given by weight.

Example I, 4 to C I The' parent cellulosic material may be a simple ormixed cellulose ether or a cellulose ester or a cellulose thiourethane,prepared for instance according to the disclosure of any one of the U.S. Patents Nos. 1,589,606, 1,683,682,

undried, i. e. moist state. In the latter case the After that time, theheating is discontinued and the reaction mass is washed in a suitablewashing apparatus, for instance on a straining cloth or in a centrifugeor the like until free from acid. This product is a degraded celluloseether or ester or thiourethane, of a very advanced stage of degradation,but is not so far degraded as to be water soluble. (Water solubledegradation products are not used because unsuitable.) The washedproduct is either dried and dissolved in caustic soda solution ordissolved therein in the water content in the moist product is to betaken into account when calculating the strength of the caustic sodasolution tobe used in the dissolving step..

The washed and dried product is mixed with so much caustic soda solutionof 9 per cent strength at 15 to 18 C., as to yield a suspension orsolution (according to the starting cellulose derivative subjected tothe hydrolyzation), containing 7 per cent of the degraded celluloseether,

which suspension or'solution respectively is free from, or contains asmall amount of undissolved constituents. Or the still wet degradedcellulose derivative is similarly treated with a proportionatelystronger NaOH solution.

According to the appearance of the suspension or incomplete solution, itis cooled down, with stirring, sufliciently to efiect solution of thedegraded cellulose ether. This may require cooling to plus 5 C., or to 00., or to minus 5 0., to minus 10 C., and maintaining the lowtemperature and agitation until solution occurs, a few minutes usuallybeing sufiicient.

A fabric, such as a woven cotton fabric is-pro- Y vided by means of asuitable machine, for ex ample a back-filling machine or a paddingmachine or a spreading machine, with one or (optionally withintermediate drying) more coatings (impregnations) of the. solution thusproduced, and the coated or impregnated or filled material, in the wetstate or after intermediate drying, is introduced into any coagulatingbath known in the viscose art. This may be the .so-called Miiller bath,for instance a bath containing per litre 160 grams of sulphuricacid'monohydrate and 320 grams of sodium sulphate, or 100 grams ofsulphuric acid monohydrate and grams of sodium sulphate, or into abathcomposed of 64 parts of water, 10 parts of sulphuric acid, 9 parts ofglucose, 12 parts of sodium sulphate, 12 parts of ammonium sulphate and1 to 3 parts of zinc sulphate, or into sulphuric acid of 10 to 20 percent strength, or into a bath-composed of 11 parts ofsodium sulphate, 14parts of magnesium sulphate, 9 parts of glucose, 1 to 3 parts ofzincsulphate and 65 to 63 parts of water, or into a 'bath consisting ofsodium carbonate solution of 20'to 28 per cent strength. The temperatureof the bath may be 45 to 50 C.

Thefabric is then washed, dried and finished in the manner common intextile finishing.

It is to be understood that the dressed textile material may be bleached(if desired or necessary) in any known manner before or after it hasbeen dried. B. Mode of procedure as in A, but with the difference that,instead of 7 per cent, the suspension or solution in caustic sodasolution of 9 per cent strength contains 9 per cent of the degradedcellulose derivative.

C. Mode of procedure as in A, but with the difference that, instead of 7per cent, the suspension or solution in caustic soda solution of 9 perExample 11, A to C The process is conducted as in Example I, A to Cexcept that, to the solution of the degraded cellulose derivative, isadded powdered talc, china clay or similar mineral filler, in an amountfrom one to two times the amount of the degraded cellulosic body. Theresulting slurry is then applied to the textile and then subjected tothe coagulating, washing, etc., steps.

Example 11!, A to C The process is conducted as in any-one of theExamples I, A to C, to II, A to C, but prior to its being applied to thetextile material, 100 to 200 per cent of a softening agent (based on the16 Example VII 1,000 parts of a simple or mixed cellulose ether orcellulose ester prepared, for example, accordi to any one of theprocesses described in the patents enumerated in Example I, A or accord-I ing to any other suitable process, are steeped in a solutioncontaining 140 parts of potassium permanganate in 20,000 parts of waterwhich have been mixed with 760 parts of a caustic soda solution of 4.5per cent strength, the mixture is well stirred and then with frequentstirring allowed to stand at 18 to C., for 4 hours. Afterwards, themixture is placed on astraining cloth or another suitable washingappliance, for example a filter press, and washed with water until freee from alkali. After having removed the excess of amount of the degradedcellulose derivative) are incorporated with the solution 'of thedegraded cellulose body. t

Example IV 1,000 parts of a simple or mixed cellulose ether or celluloseester (prepared for example according to one of the processes describedin the patents enumerated in Example I, A, are mixed or kneaded at 18 to20 C., for 6 to 12 hours in a suitable apparatus, for example aWerner-Pfleiderer shredder or akneading machine with 5,000

' to 10,000 parts of sulphuric acid of 55 to 60 per cent strength addedat 15 C. After thattime, the reaction mass is washed with water, (hot orcold), for example on a straining cloth or in a centrifuge or the likeuntil free from sulphuric acid.

The product thus obtained is dissolved in dilute caustic soda solution,and the solution applied to textile: materials, e. g. as described inExample I, A to v i Example V 1,000 parts of a simple or mixed celluloseether or'cellulose ester (prepared, for example, according to anysuitable one of the processes described in the patents enumerated inExample I, A) are mixed in a suitable vessel with 20,000 to 30,000

water by pressing or centrifuging, the residue is mixed with 2300 to2400 parts of caustic soda solution of 18 per cent strength, and themixture slowly heated to C., with constant stirring and allowed to standat 18 to 20 .C. for 12 to 36.

hours. After that time, and if desired after previous dilution withwater, the mixtureis acidified with dilute sulphuric acid or with anyother suitable acid and then decolorized in known manner. This, forinstance, may be performed by passing gaseous-S02 into the mixture or byadding sodium bisulphite in the solid or dissolved state to the mixtureuntil the mixture becomes colorless. The product of the reaction is thenwashed and, if desired, dried in a suitable manner.

The product thus obtained is then dissolved and the solution applied toa textile material as described in Example I, A to C.

Example VIII Mode of procedure as in Example VII, but with the exceptionthat no caustic soda solutionis added to the potassium permanganate andthat, instead of at room temperature, the oxidation is carried out at 90to 100 C., the duration being 1 hour. i

Example IX The process is conducted as in Examples VII or VIH, but withthe difference that the treatment of the reaction product with thecaustic soda solution at 50 C., is omitted, and that the washed parts ofa solution of chloride of lime (bleaching powder) of 4 B. to 10 B. untilthe mixture is homogeneous and allowed to stand at room temperature for12 to 24 hours. After that time, the mass is washed in a suitablewashing apparatus, for instance on a straining cloth or in a centrifugeuntil free from chlorine, then acidified with a weak organic acid, forexample acetic acid of 3 to 5 per cent strength and then freed from theacetic acid by washing it again.

The product may be dried and in the dried or moiststate dissolved incaustic soda solution and the solution applied to a textile material asdescribed in Example I, A to C.

Example VI- product, if desired after appropriate dilution, for instancewith water, is decolorized with sulphurous-acid as described in ExampleVII.

'The sizing yarn will be readily understood from the foregoing examples.

It is of course well known that heretofore, in the manufacture ofcellulose ethers of, the alkalisoluble varieties including those whichwill readily dissolve in dilute NaOH solution at or near the freezingpoint (e. g. --10-to +5 C.), as well as those which dissolve thereinonly at or near the freezing point (i. e. 10 to +5 C.), a very smallamount of degrading of the cellulose or of the ether has occurred. Butin such processes, the aim has been to prevent any such degree ofdegrading as would materially injure the film-forming property of thecellulose ethers and the quality of the products. Thus in U. S. Patent1,589,606, alkali soluble ethers of cellulose are prepared, and in theetherification step, heat is applied. British Patent 374,964 producescellulose ethers which dissolve in refrigerated caustic alkali solution,by a process in which no extraneous heat is employed in theetherification operation. Both of these two kinds of cellulose ether arecapable of forming strong flexible films. But the process of the Britishpatent gives ethers I 17., which, in the form of films, have a muchhigher degree of flexibility, toughness and tenacity (illustrated bymuch higher Schopper fold test) than ethers of said U. S. patent. Thishigher quality of the films produced in the British patent is be-.

. ble of giving coherent films, or films that do not disintegrate,either in the coagulating bath, or

in the washing bath or in the drying step, and at the same time thedegrading is not carried sufiiciently far to give principally watersoluble products.

Owing to the fact that the cellulose ethers are degraded too far toproduce coherent films, they do not substantially increase the stifinessof the textile material under treatment, i. e., they give a soft finish,as compared with the stiff finish of the said prior patents.

The term degraded as used in th present specification and the appendedclaims in connection with the cellulose derivatives (ethers etc.)treated in accordance with the pre's'ent invention, is intended toinclude cellulose ethers degraded to the extent indicated. Such degradedproducts have a lowered solution viscosity compared with a standardsolution of substantially undegraded cellulose ether.

A solution of standard hydroxy ethyl cellulose ether, (film formingether), was prepared as follows, (all parts are by weight).

100 parts of air dry wood pulp were steeped for 45 minutes in a largeexcess of an aqueous 19% sodium hydroxide solution, at room temperature,and the moist alkali cellulose then pressed to 270 parts by weight. Thepressed material was comminuted in a shredding machine at 17 to 18 0.,for 50 minutes and allowed to stand at 23 0., for 6 hours and 25minutes. The aged material was then mixed in the shredder with 16.1parts of ethylene chlorohydrin for 2 hours and 30 minutes at 19-20 0.,without any extraneous heat being applied. The mass was allowed to standat 23 0., for 21 hours and 30 1 minutes. The material was purified bywashing with water at 7580 C. After centrifuging 'and drying, thematerial contained 7.72% moisture.

up to room temperature. At 25 0., the viscosity 4 of this solution was20.2 times that of pure glycerol. This viscosity was taken as 1.0 as astandard.

A portion of this solution was spread on glass plates to a depth of0.015 inch. The plates, carrying this film or solution, were placed in10% sulphuric acid solution at room temperature for five minutes inorder to coagulate the ether. The

resulting films were removed from the plates,

'lulose prepared as described were mixed with 2,000 parts of 0.5%hydrochloric acid solution at room temperature and heated to 0., during35 minutes and kept at 100 0., for 30 minutes. The material wasseparated from the acid by filtration, washed free of acid with water atroom temperature, and allowed to air-dry until the moisture content was6.0%.

7 parts of the dried material (water-free basis) were mixed with 9 partsof solid sodium hydroxide and sufficient water to make 100 parts, thenchilled to 0 0.. with stirring, (to eifect solution of the degradedether), and the solution was allowed to warm up to room temperature.

Portions of this solution were spread on a glass plate to a depth of0.015 inch. ,The plate was immersed in 10% sulphuric acid for fiveminutes to coagulate the degraded ether. When removal of the film fromthe plate was attempted, the film disintegrated. Small fragments of thefilm could be removed, but these disintegrated quickly when an attemptwas made to wash them in water. v

The solution viscosity of the degraded product was'tested at 25 0., andfound to be 0.0043 as compared with that of the above mentionedsubstantially undegraded standard hydroxy ethyl cellulose ether taken asunity.

This degraded product was found to be insoluble, (a) in water at roomtemperature and (b) in a mixture comprising 50% water and 50% ethylalcohol at room temperature.

Various modifications of thisdegrading treatment were tried out(diiferent concentrations of acid, different temperatures of treatment,and diiferent time periods). It was found that if the ether is so fardegraded that the solution viscosity is. not over one-tenth of that'ofthe substantially undegraded ether (1 e. the standard ether), thedegrading is suflicient to be fairly satisfactory for the presentinvention, and when the ether is so far degraded that its solutionviscosity is below one-tenth of that of the standard (substantiallyimdegraded) ether, it is 'so far degraded that coherent films cannot bemade by the steps of spreading into a sheet, coagulation,

washing and drying, applied to the caustic alkali solution of thedegraded'ether.

But for the best results, the degradation of the cellulose ether ispreferably carried so far that the solution viscosity of the degradedether is between 0.002 and 0.01 times that of the substantiallyundegraded ether.

Degrading to a solution viscosity of below 0.002 times that of theundegraded ether, so long as too great a portion of the ether does notbecome water soluble, does not appear to do any harm.

The term fibrous material" used in the specification and claims is,wherever thecontext permits, intended to include any material consistingof, or containing fibres, such as loose fibres, whether vegetable oranimal or artificial or mixed, of any kind and in any form, or textilematerials as herein defined or paper at any stage of its preparation,paper pulp included.

The expression .textile material in the specificatlon andclaims'includes, wherever the context permits, any spun or woven textilefibres, whether animal or vegetable (for example, silk, fiax, linen,hemp, ramie, Jute, wool and particularly cotton) as. vweilas artificialfibres of any kind (for example, artificial silk or artificial cotton orartificial wool or staple fibre, any one of them in the form of yarn orfabrics or knitted goods consisting of or containing artificial fibres)in short'every type of finish produced by coating or treating the wholeor part of the surface of, or incorporating with, or introducing into,the totality or part ofthe. fibrous materials as herein defined ingeneral or textile materials as herein defined; in particular one ormore organic materials that may or may not contain one or more inorganicmaterials. Y

The expression finishing is, wherever the context permits, intended toinclude any process or method or operation capable of producing a finishas herein defined.

The expression finishing material" used in the specification and claimsis, wherever the context permits, intended to include any organicmaterial by itself or in conjunction with one or more inorganicmaterials suitable for the production of any finish as herein defined.

The expressions applying? and applicationas used in this specificationincludes, wherever the context permits, any manner of application,whether manual or mechanical, such as is customary in dressing, sizing,filling. weighting. pregnating, finishing, coating, printing orstencilling fibrous materials as defined above, whether yarn or fabrics.

The expression filler used in the specification and claims is, whereverthe context permits, intended to include an organic or inorganicsubstance which is added in the solid form to a finishing material asherein defined and which is insoluble in the finishing material'or inits solutions or dispersions or pastes or magmas or suspensions andwhich is evenly or unevenly distributed in the finishing material and inthe finish as herein defined.

The term ce1lulose" used in the description and claims is, wherever thecontext permits, intended to include cellulose, its conversion andoxidation products, such as cellulose hydrate, hy-

. drocellulose, oxycellulose, acid cellulose and the like, in short, anybody of the cellulose group which has been proposed as starting materialfor the preparation-of cellulose derivatives or cellulose compounds ofany kind.

In the specification and claims, wherever the context permits, theexpressions "alkali-soluble cellulose ether, "cellulose ether which issoluble or partially soluble or incompletely soluble in;

at room temperature and/or at a lower temperature, for example ata'temperature between room temperature and 0 (3., Or lower and suchsimple or mixed cellulose ethers and such cellulose etheresters ascannot be completely or incompletely or partially dissolved in causticalkali solution at room temperature, but as can be dissolved ordispersed or incompletely or partially dissolved or dispersed in causticalkali solution by cooling their mixtures with, or suspensions orincomplete solutions in, caustic alkali solution to a temperaturebetween room temperature and 0 0.. or to 0 C., or to a temperature below0 0,, for example to minus 5 C., or to minus 10 C., or lower, and suchsimple or mixed cellulose ethers and such cellulose ether-esters ascannot be completely or incompletely or partially dissolved in causticalkali solution at room-temperature or at a temperature between roomtemperature and 0" 0.. or even at 0 C.-, but as can be dissolved ordispersed or incompletely or partially dissolved or dispersed in causticalkali solution by cooling their mixtures with, or suspensions orincomplete solutions in, caustic alkali solution to a temperature below0 C., e. g. to temperatures at which freezing or formation of crystalsoccurs,'for example minus 5 or minus 10 C., or minus 15 to 20 C., ormore, included.

Wherever the context permits, the term alkali cellulose" means alkalicellulose prepared in the usual manner, namely by steeping cellulose incaustic alkali solution and removing the excess of the latter bypressing, or by mixing cellulose with such an amountof caustic alkalisolution or with such amounts of caustic alkali and water as are desiredto be present in the final alkali cellulose.

The expression etherification used in the specification and claimscovers alkylation or aralkylation or hydroxyalkylation or production ofhydroxy-acid derivatives (ethers) ether covers simple alkyl'or aralkyland hydroxy-alkyl or hydroxy-acid ethers and also mixed ethers, forexample the mixed ethers hereinbefore set forth, etherifying agentscovers alkylating and aralkylating and hydroxy-alkylating agents andhalogen fatty acids.

The term hydroxy-alkyl" is intended to include the introduction ofhalogenated or nonhalogenated hydroxy-alkyl radicals, or dior polyvalentalcohols in conjunction with one or kylating agents that containunsubstituted or substituted (for example aralkyl groups) alkyl groups.

The term hydroxy-alkylating agen is, wherever the context permits,intended to include halogen derivatives of dior polyhydric alcohols,particularly halohydrins, such as monohalohydrine and alkylene oxides.

-. In the specification and claims the expression "halogen fatty acids"or "monohalogen fatty acid includes, wherever the context permits,

monochlor-, monobromand mono-iodo-fatty acids themselves, theirderivatives (such as esters) and their salts, as well as substances andmixtures of'substances which yield monohalogen fatty acids or theirderivatives.

In the appended claims, the term "liquid dispersing agent" is used in 'abroad sense to include liquid media in which the hydrolyzed, oxidized ordegraded cellulosic bodies can be colloidally dispersed and/or partly orwholly dissolved.

In the appended claims, the term "oxy-organo derivative of cellulose" isintended to cover both ethers and esters, i. e. bodies in which ahydroxyl hydrogen atom of the cellulose molecule has been substituted byan organic radical (substituted or unsubstituted) It has beendemonstrated that the alkaline solution of the degraded celluloseethers, with or without mineral fillers, can be kept for long periods,at atmospheric temperatures. According- 1y it is entirely feasible for afactory to prepare such solutions, and to ship these to a textiledressing plant.

While caustic soda solutions of 7 to 9% concentration, and containing 7to 12% ofthe degraded cellulose ether, are referred to above, it is tobe understood that more dilute or more concentrated solutions can beused, e. g. NaOH solutions of 4 to 15% containing about 3 to of thedegraded cellulose ether. Generally it is advisable to use as low aconcentration of the caustic alkali as will dissolve the desired amountof the degraded cellulose ether.

This application is a continuation-in-part of copending applicationSerial No. 228,715 filed September 6, 1938. The herein described processof treating textiles with the xanthated degraded cellulose ethers andthe making of such xanthated products are claimed in another applicationSerial No. 469,841, flled concurrently herewith. 1

What is claimed is: I j

1. A process of finishing a textile material which comprises applyingthereto a dispersion in an aqueous caustic alkali solution, of a de--graded cellulose derivative whichis at least partially soluble in suchcaustic alkali solution, but insoluble in water, and in aqueous alcohol,and which degraded cellulose derivative has a solution viscosity lessthan one-tenth of that of the corresponding substantially undegradedfllmforming cellulose derivative having the same ratio of the samesubstituent radical, under like conditions, and coagulating saiddegraded cellulose derivative on said textile material in the form ofdiscrete particles, the cellulose derivative being one selected from thegroup consisting of cellulose ethers, cellulose esters, celluloseether-esters and cellulose thiourethanes, said degraded cellulosederivative'being so far degraded as to be incapable of forming acoherent film which does not disintegrate when a. thin layer of thealkaline solution thereof is subjected to the series of steps,coagulating, washing and drying.

2. A process as in claim 1, in which the degraded cellulose derivativehas a solutiorfviscosity between about 0.002 and 0.01 times that of thecorresponding substantially undegraded cellulose derivative under likeconditions.

3. A process as in claim 1, in which the degraded cellulose derivativeis a hydroxy-alkyl ether of cellulose.

4. A process as in claim 1, in which the dispersion of degradedcellulose derivative includes persion oi the degraded cellulosederivative is printed upon the textile material.

6. A process which comprises degrading an alcohol insoluble, alkalisoluble, water insoluble oxy-organo derivative of cellulose whichinitially is capable of yielding a strong flexible film by introducing athin uniform layer of a solution thereof in dilute caustic alkalisolution into an acid coagulating bath, washing and drying, and whichcellulose derivative initially has a high solution viscosity, whichprocess comprises subjecting such cellulose derivative to the action ofa degrading agent until the solution viscosity of the so treatedcellulose derivative has fallen to below one-tenth of that of asubstantially undegraded oxy-organo derivative of cellulose having thesame ratio of the same substituent organic radical, and discontinuingthe action of such degrading agent while the major part at least of saidoxy-organo derivative of cellulose is still insoluble in water and inalcohol but capable of being dissolved in dilute caustic alkalisolution, thereafter dissolving such degraded product in caustic alkalisolution of about 3% to about 14% concentration, impregnating a, textilematerial therewith, coagulating the degraded oxy-organo derivative ofcellulose in the form of discrete particles on and in said textilematerial.

'7. A process of dressing a textile material which comprisesimpregnating a textile material with a dispersion in a caustic alkalisolution of a water insoluble degraded oxy-organo derivative ofcellulose, which has been so far degraded a coloring agent and thetextile material is that its solution viscosity is substantially belowone-tenth of that of a substantially undegraded oxy-organo derivative ofcellulose which contains the same ratio of the same substituent organicradical, and thereafter coagulating the degraded oxy-organo derivativeof cellulose in the form of discrete particles on and in said textilematerial.

8. A process of dressing a textile material which comprises impregnatinga textile material] with a dispersion-in a caustic alkali solution of adegraded oxy-organo compound of cellulose, which latter is substantiallyidentical with the degraded product produced by the process of claim 22,and coagulating the degraded oxy-organo compound of cellulose, in theform of discrete particles on and in said textile material.

9. A process as set forth in claim 6, in which the degrading agent is adilute mineral acid,

10; A process as in claim 6, in which the degrading agent has oxidizingproperties.

11. A process of treating a textile material which comprises mixing witha caustic alkali solution, a degraded cellulose ether which is insolublein water but of which at least a substantial part is soluble in dilutecaustic alkali solution, and which degraded cellulose ether is ofapproximately the same degree of degradation as the herein describedproduct obtained by mixing a water-insoluble alkali-soluble celluloseether of a low degree of etheriflcation with 20 to 30 times its weightof hydrochloric acid solu tion of 0.05% to 2% strength and heating themixture to 50 to 0., for between half an hour and four hours, finishingthe textile material with the mixture so produced, and thereaftertreating the so dressed textile material with a coagulating agent.

12. A process which comprises applying to a textile material, analkaline solution of a degraded cellulose ether which is insoluble inwater and capable of being dissolved by a, NaOH soluand then subjectingthe textile material with v the solution carried thereby, to the actionof a coagulating agent for said degraded cellulose ether, said degradedcellulose ether having a degree'oi! degradation substantially equal tothat of a water insoluble product produced by heating a substantiallyun'degradcd water insoluble alkali soluble cellulose ether with to timesits weight of hydrochloric acid solution of 0.5% strength for a periodbetween a half hour and four hour-s at 50 to 100 C., and then washinguntil acid-free.

13. Textile material carrying," intimately bonded thereto, a dressingconsisting of discrete particles of a degraded water insoluble alkalisoluble oxy-organo derivative of cellulose, said degraded derivative ofcellulose being so far degraded that it cannot be made into a coherentfilm by the process of introducing athin sheet of an alkaline solutionof the cellulose derivative into an acid setting bath, washing theproduct and drying the same, and said degraded cellulose V derivativebeing-one selected from the group consisting of cellulose ethers,cellulose esters, cellulose ether-esters and cellulose thiourethanes,such degraded cellulose derivative being insoluble in water but at leastpartially soluble in dilute caustic alkali solution, ,4

14. A product as in claim 13, which also carries a coloring matter.

15. A product as in claim 13 in which the degraded cellulose derivativeis a degraded hydroxyalkyl cellulose ether.

16. A product as in claim 13 in which the degraded cellulose derivativeis so far degraded that its solution viscosity is between 0.01 and 0.002

times that of thecorresponding substantially undegraded cellulosederivative containing the same ratio or the same substituent groups,under like conditions.

17. As an agent for treating textile materials, the herein describedliquid which comprises a dispersion in an aqueous caustic alkalisolution, of a degraded cellulose derivative which contains a celluloseresidue and which is degraded to the extent specified in claim 1.

18. A process for the manufacture of a new degraded cellulose etherhaving the characteristics that it is at least partially soluble ordispersible in dilute caustic alkali solution and substantiallyinsoluble in water and which is brittle and friable when dry, andincapable of forming froma thin layer of a solution thereof in dilutecaustic alkali solution, coherent films which do not disintegrate in anacid coagulating bathor in the washing water whereinto it is introducedfrom the said coagulating bath or on being dried, and which degradedcellulose ether is incapable of forming films which are suitable forpractical use as films, which process comprises treating an alkalisoluble water insoluble cellulose ether capable of forming a coherentfilm and which ether is substantially insoluble in strong alcohol andindilute alcohol, with a degrading agent capable of degrading thecellulose molecule, and continuing said treatment until a product isformed which has the aforesaid characteristics, and stopping saidtreatment while a major portion of the ether remains substantiallyinsoluble in water and in strong alcohol and in dilute alcohol and atleast partially dispersible'in caustic alkali solution,

19. A process for the manufacture of a new degraded cellulose etherhaving the characteristics that it is at least partially soluble ordispersible in dilute caustic alkali solution and substantiallyinsoluble in water and in alcohol and which is too far degradedto yieldcoherent films but breaks up into particles by introducing a thinuniform layer of the alkaline solution of such ether into an acidcoagulating bath or in the washing water whereinto it is introduced fromthe said coagulating .bath or on being dried, and which degraded etheris too far degraded'to be capable of forming films which are suitablefor practical use as films, which process comprises treating an alkalisoluble water insoluble alcohol insoluble film-forming cellulose etherwith a degrading agent, continuing said treatment until a degradedcellulose ether remains which is dew tially insoluble in water and inalcohol and which is incapable of forming colrerent' films by treating athin layer of its alkaline solution with an acid setting bath, which donot disintegrate in the said acid bath or in the washing water whereintoit is introduced from the said acid bath or on being dried, and whichdegraded cellulose ether is incapable of forming films which aresuitable for practical use as films, which process comprises treating analkali soluble water insoluble alcohol insoluble film-forming celluloseether with a degrading agent, continuing said treatment until degradingof thecellulose ether has sofar progressed that the degraded'celluloseether becomes incapable of forming coherent films by treating a thinlayer of its alkaline solution with an acid setting bath, which do notdisintegrate in the said acid \bath or in the washing water whereinto itis introduced from said setting bath or on being dried and whichdegraded cellulose ether is incapable of forming films which aresuitable for practical use as films, and then stopping such treatmentwhile at least the major part of the degraded cellulose ether remainsinsoluble in water and in alcohol but at least partly soluble inrefrigerated caustic soda solution of 3 to 14% concentration.

21. A process as covered in claim 20 in which the degrading agent is adilute acid.

22. A process for the manufacture of a new degraded oiLv-organo compoundof cellulose having the characteristics that it is at least partiallysoluble and dispersible in refrigerated dilute caustic alkali solutionand substantially insoluble in water and in alcohol and which is too fardegraded to be capable of iorming coherent films integrate in the saidcoagulating bath or in the washing water whereinto it is introduced fromsaid coagulating bath or on being dried, and which degraded oxy-organocompound of cellulose 'is incapable of forming films which are suitablefor practical use as films, which process comprises treating an alkalisolubile water insoluble alcohol insoluble oxy-organo compound ofcellulose capable of forming a coherent film, with a degrading agent,continuing said treatment until the oxy-organo compound of cellulose beecomes so far degraded that it remains insoluble but capable of at leastpartly dissolving in refrigerated dilute caustic alkali solution.

23. A process as claimed in claim 18, wherein the degrading agent usedfor treating the cellulose ether is a substance having acid properties.

24. A process as claimed in claim 18 wherein the degrading agent usedfor treating the. cellulose ether is a substance having an oxidizingaction.

, 25. A process as claimed in claim 18, wherein the cellulose ether usedis a mixed ether which is substantially insoluble in water but which canbe dissolved in dilute caustic alkali solution under refrigeration,

26 tween 0.002 times and 0.01 times that of the correspondingsubstantially undegraded cellulosecompound, and which product isinsoluble in. wa-

ter, insoluble in strong alcohol and insoluble in dilute alcohol, and atleast partly soluble in a refrigerated dilute aqueous solution ofcaustic alkali, which'product is friable and brittle.

'26. A deeply degraded cellulose ether which is substantially insolublein water and in dilute acids at all temperatures, and insoluble inorganic solvents, and which canreadily be disorgano compound ofcellulose, which is insoluble in water-and in alcohol and in acetone andin dilute alcohol and in dilute acetone, but which will at least partlydissolve in'dilut'e causticalkali solutions under refrigeration, andfrom a solution of which compound in caustic alkali solutionacidification will coagulate said degraded cellulose derivative, suchproduct being too far degraded to form a coherent film by the series ofsteps of treating a thin uniform layer of the alkali solution thereofwithan acid coagulating bath, then washing and then drying, suchcellulose derivative in the dry state being friable and brittle.

28. A product as claimed in claim 26, which has,

a solution viscosity of substantially 'below onetenth of that of asubstantially undegraded cellulose ether having the same content of thesame alcohol radical substituted for hydroxyl hydrogen.

lulose, which product is soluble in dilute caustic alkali solution,which product has a. solution viscosity below one-tenth of that of thesubstantially undegraded cellulose compounds having the same proportionof the same organic substituent radical, and which product is insolublein water, insoluble in strong alcohol and insoluble in dilute alcohol,and which product is friable and brittle.

30. A degraded cellulose ethenwhich product has a solution viscositybelow one-tenth of that of the corresponding substantially undegradedcellulose ether,and which product is insoluble in water, insoluble instrong alcohol and insoluble in dilute alcohol, and at least partlysoluble in a refrigerated dilute aqueous solution of ca tic alkali,which product is friable and brittle.

29. A degraded oxy-organo compound of eel-- 31. A degraded oxy-organocompound of cellulose, which product has a solution'viscosity be- 32.As-a nov'el sizing material for the dressing of textiles, a deeplydegraded ,water insoluble alkali soluble cellulose ether, dissolved indilute aqueous caustic alkali solution, such degraded cellulose ether,when in the solid state having the properties as set forth inclaim 26.

33. A process of degrading a water insoluble,

alcohol insoluble cellulose ether of a kind whichis capable of beingdissolved in a dilute aqueous caustic alkali solution to give .acellulose ether solution from which high quality strong, flexible filmscan be produced by subjecting a thin layer of an aqueous alkalinesolution of such ether to,

the action of an acid coagulating bath, washing and drying, whichprocess comprises. subjecting such a cellulose ether to the action of areagent capable of dcgradingcellulose, and continuing such treatmentuntil the treated ether no longer has the property of giving a coherentfilm. by subjecting a thin layer of an alkaline solution thereof to theaction of an acid coagulating bath, washing and drying, but stoppingsuch treatment with such reagent while the major part at least of saidcellulose ether remains insoluble in water and in alcohol and-thereafterwashing such degraded cellulose ether with water until substantiallyfree from water soluble constltutentss 34. Aprocess as in claim 33 inwhich the reagent for producing degradation of the cellulose ether is adilute 'mineral acid.

35. A process as in claim 33, in which the degrading agent has oxidizingproperties,

36.. A process of degrading a cellulose. ether which has a high solutionviscosity, which ether is insoluble in water and in such organicsolvents as are capable of dissolving highly etherifled 'ethers ofcellulose and which initial ether is capable of being converted into astrong flexible film by bringing a thin uniform layer of a solution ofthe ether in dilute aqueous caustic alkali solution into contact with abath of 'anacid coagulating solution, washing and drying, which processcomprises treating such an ether with a degrading agent until thesolution viscosity of the said ether has fallen to below one-tenth ofthat of a substantially undegraded cellulose ether stituent radical, anddiscontinuing such treatment with the degrading agent beforethe majorpart of the said cellulose ether becomes soluble in water and while thesaid ether remains capable of being dissolved in dilute caustic alkalisolution.

37. A process as in claim 36, in which the de- I grading agent is adilute mineral acid.

38. A process as in claim 36, in which the degrading agent has oxidizingproperties.

39. A deeply degraded cellulose ether which is substantially insolublein water and in dilute acids at all temperatures, and insoluble inorganic solvents, and which can readily be dispersed in caustic alkalisolution under refrigeration, and of which a substantial part at leastwill dissolve in caustic alkali solution under refrigeration, and whichcellulose ether is too far degraded to produce a coherent film by thesteps of subjecting a thin layer of its solution in caustic .alkalisolution to coagulation, washing and dryproperties as and is of the samedegree of degradation as the herein described Product ohtained by mixinga water-insoluble alkali-soluble cellulose ether of'a, low degree oretherification with 20 to 30 times its weight of hydrochloric acidsolution of 0.05% to 2% strength and heating the mixture to v50 'to 1000., for between half an hour and four hours, and washing out the watersoluble constituents from the treated cel1u-' lose ether.

Aldministratfla: C. T. A. of the Estate of Leon Liltenfeld, Deceased.

. 28 REFERENCES CITED The following references are of record in the fileof this patent:

UNITED STATES PA'I'ENTS Number Name Date 1,950,664 Dreyfus et a1 Mar.13, 1934 2,087,237 Bolton July 20, 1937 2,157,530 Ellsworth et al. May9, 1939 Richter Nov. 27, 1906

